Color photographic material

Abstract

A color photographic material containing at least one silver halide emulsion layer sensitised for the red range of the spectrum, which material contains at least one compound of the formula (I) in which R11 and R12 mutually independently denote an electron-attracting group, X11 denotes H or a group seperable on reaction with the developer oxidation product, Y11 denotes a group to complete a nitrogenous heterocycle, providing that a group represented by R12 is attached to a carbon atom of the heterocycle, n denotes 1 or 2, and at least one compound of the formula (II) in which R21 denotes alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamino, acyloxy, hetaryl, halogen, nitro or cyano, R22 denotes OH or has the same meaning as R21, n,m mutually independently denote 0 or 1, o denotes 0, 1, 2, 3, 4 or 5, providing that the compound contains a total of at least 16 C atoms, is distinguished by improved light stability.

Description

This invention relates to a colour photographic material containing an emulsified heterocyclic cyan coupler from the group of pyrazoloazoles and certain coupler solvents.

It is known to produce coloured photographic images by chromogenic development, i.e. by developing silver halide emulsion layers exposed with an image by means of suitable chromogenic developer substances, so-called colour developers, in the presence of suitable colour couplers, wherein the oxidation product of the developer substance, which oxidation product is produced congruently with the silver image, reacts with the colour coupler to form a dye image.

Naphtholic or phenolic cyan couplers are conventionally used to produce the cyan component colour image. The latter have hitherto been preferred in colour photographic print materials due to the more favourable absorption (at approx. 660 nm) and greater dark storage stability of the image dyes produced therefrom on chromogenic development.

However, in comparison with the image dyes produced from conventional pivaloylacetanilide yellow couplers and pyrazolotriazole magenta coupler, the dark storage stability is inadequate. Moreover, the phenolic cyan dyes have a relatively large half-width, which gives rise to a distinct, unwanted absorption in the green range of the spectrum.

In order to eliminate these disadvantages it has been proposed, inter alia in EP 717 315, to use specially substituted pyrazoloazoles as cyan couplers. However, in conventional coupler solvents, the dyes produced from these couplers exhibit an unwanted shift of the absorption flank towards shorter wavelengths. Excessively low light stability is another disadvantage.

The object of the present invention was to provide colour photographic materials containing pyrazoloazole cyan couplers which are distinguished by improved light stability and which simultaneously exhibit thermal stability. A further object was to provide cyan couplers having colour reproduction which is distinctly improved in comparison with known prior art materials.

The present invention provides a colour photographic material containing at least one silver halide emulsion layer sensitised for the red range of the spectrum, which layer contains associated therewith at least one compound of the formula (I)

in which

R11 and R12 mutually independently denote an electron-attracting group,

X11 denotes H or a group seperable on reaction with the developer oxidation product,

Y11 denotes a group to complete a nitrogenous heterocycle, providing that a group represented by R12 is attached to a carbon atom of the heterocycle,

n denotes 1 or 2,

and at least one compound of the formula (II)

in which

R21 denotes alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamino, acyloxy, hetaryl, halogen, nitro or cyano,

R22 denotes OH or has the same meaning as R21,

n, m mutually independently denote 0 or 1,

o denotes 0, 1, 2, 3, 4 or 5, providing that the compound contains a total of at least 16 C atoms.

For the purposes of the present application, alkyl should be taken to mean linear or branched, straight-chain or cyclic, substituted or unsubstituted hydrocarbon groups, preferably alkyl groups having 1 to 32 C atoms. Open-chain alkyl groups which may be considered are in particular methyl, ethyl, n-propyl, n-butyl, n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl, while branched alkyl residues are in particular 2-hexyl-decyl, 2-octyldodecyl and 2-ethylhexyl residues. Preferred cycloalkyl groups are cyclohexyl, in particular 4-t.-butylcyclohexyl, 2,6-di-t.-butyl-4-methylcyclohexyl. For the purposes of the present application, alkenyl should be taken to mean linear or branched cyclic or straight-chain substituted or unsubstituted unsaturated hydrocarbon residues, such as for example ethenyl, 2-propenyl, isopropenyl and oleyl. For the purposes of the present application, aryl should be taken to mean aromatic hydrocarbons, wherein phenyl or naphthyl is preferred. These may be both substituted and unsubstituted. For the purposes of the present application, hetaryl should be taken to mean aromatic systems which contain at least one heteroatom. These also preferably comprise 5- or 6-membered ring systems, which may present not only as monocyclic but also as fused ring systems. The ring systems may in this case be both substituted and unsubstituted ring systems. Heteroatoms which may in particular be considered here are N, S and O. A ring system may preferably have between 1 and 3 heteroatoms, wherein the heteroatoms may be identical or different. In the case of fused ring systems, two or more identical or different heterocyclic systems may be fused, as well as hetaryls with arylene. Typical examples are: pyridine, pyridazine, pyrimidine, pyrazine, oxazole, isoxazole, thiazole, 3,4-oxadiazole, 1,2,4-oxadiazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, in particular furan, pyrrole, thiophene and indole.

For the purposes of the present application, alkoxy should be taken to mean residues of the formula OR′, wherein R′ denotes an alkyl residue in accordance with the above-stated definition.

For the purposes of the present application, aryloxy should be taken to mean residues of the type OR″, in which R″ denotes an aryl residue in accordance with the above-stated definition.

For the purposes of the present application, acyl should be taken to mean an aliphatic, olefinic or aromatic carboxylic, carbonic, carbamic, sulfonic, amidosulfonic, sulfinic, phosphoric, phosphonic or phosphonous acid residue.

For the purposes of the present application, substituents which may be considered are aryl, alkyl, alkoxy, aryloxy, acyl, acyloxy, acylamino, hetaryl, alkynyl, hydroxy, cyano, carboxy, sulfo and halogen, such as preferably fluorine, chlorine or bromine.

For the purposes of the present application, an electron-attracting group is an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogen-ated aryloxy, aryloxy, acyl sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkyl-sulfonylmethyl, arylsulfonylmethyl or a nitro group, as well as a halogen atom.

Seperable groups X11 may comprise halogen, for example chlorine, N-linked, optionally substituted N-heteroaromatics, for example pyrazoles, imidazole, triazoles or non-aromatic heterocyclics, for example hydantoins, oxazolidinediones, S-linked aliphatic or aromatic mercaptans, for example mercaptopropionic acid, 2-acylamino-phenyl mercaptans, or O-linked aliphatic or aromatic hydroxy compounds, for example ethylene glycol, p-salicylic acid ethyl ester.

Preferably used compounds of the formula (I) are those of the formula (I-A)

in which

R13 and R14 mutually independently have the meaning of R11 or R12,

X12 has the meaning of X11 and

Z12 denotes H or a substituent.

In the compounds of the formula (II), R21 preferably denotes alkyl, alkoxy, alkylamino, acyl, acylamino, acyloxy, hydroxy or halogen, n and m preferably denote 0 or 1, providing that n and m are not simultaneously 1, o denotes zero, 1 or 2 and p denotes zero, 1, 2 or 3. Particularly preferred compounds of the formula (II) are those of the formula (II-A)

in which

R23, R24 mutually independently denote alkyl, acyl, acylamino, alkoxy, halogen, cyano or nitro,

R25 denotes H or alkyl,

R26 denotes H, alkyl or acyl and

r, s mutually independently denote 0, 1 or 2.

Table 1 below lists some particularly preferred compounds of the formula (I) or (I-A) by way of example.

R13 R14 X12 Z12 I-1 H H I-2 —S—CH2—CH2—COOH H I-3 Cl H I-4 H H I-5 H I-6 C16H33—O—CO—CH2—CH2—NH—CO— H H I-7 C12H25—SO2—C3H6—NH—CO— —CF3 H I-8 H H I-9 H H I-10 C18H37—NH—SO2— H H I-11 —CN H H I-12 H H I-13 H I-14 H H I-15 t-C4H9—NH—CO— H H and 50/50 wt. % I-16 —CN —S—CH2—CH2—COOH H I-17 H H I-18 H H I-19 H H I-20 H H

Some examples of the formula (II) or (II-A) which are particularly preferred according to the invention are listed below.

Examples of compounds according to the invention of the formula (II) are

The compounds according to the invention of the formulae (I) and (II) may be used in the photographic material in conventional quantities. The compounds of the formula (I) are preferably used at a rate of 20 to 2000 mg/m2 of the photographic material, in particular of 50 to 500 mg/m2 of the photographic material. The compounds of the formula (II) are preferably used in a weight ratio of 20:1 to 1:10 relative to the compounds of the formula (I), in particular in a weight ratio of 10:1 to 1:5 and particularly preferably in a weight ratio of 5:1 to 1:2.

The compounds according to the invention of the formulae (I) and (II) are preferably used in a red-sensitised silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer. The compounds of the formulae (I) and (II) are in particular used in the same layer.

Examples of colour photographic materials are colour negative films, colour reversal films, colour positive films, colour photographic paper, colour reversal photographic paper, colour-sensitive materials for the dye diffusion transfer process or the silver dye bleaching process. A review is given in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).

The photographic materials consist of a support onto which at least one photosensitive silver halide emulsion layer is applied. Thin films and sheets are in particular suitable as supports. A review of support materials and the auxiliary layers applied to the front and reverse sides of which is given in Research Disclosure 37254, part 1 (1995), page 285 and in Research Disclosure 38957, part XV (1996), page 627.

The colour photographic materials conventionally contain at least one red-sensitive, one green-sensitive and one blue-sensitive silver halide emulsion layer, optionally together with interlayers and protective layers.

Depending upon the type of the photographic material, these layers may be differently arranged. This is demonstrated for the most important products:

Colour photographic films such as colour negative films and colour reversal films have on the support, in the stated sequence, 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, magenta-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers. The layers of identical spectral sensitivity differ with regard to their photographic sensitivity, wherein the less sensitive sub-layers are generally arranged closer to the support than the more highly sensitive sub-layers.

A yellow filter layer, which prevents blue light from reaching the underlying layers, is conventionally located between the green-sensitive and blue-sensitive layers.

Possible options for different layer arrangements and the effects thereof on photographic properties are described in J. Inf. Rec. Mats., 1994, volume 22, pages 183-193 and in Research Disclosure 38957, part XI (1996), page 624.

Colour photographic paper, which is usually substantially less photosensitive than a colour photographic film, conventionally has on the support, in the stated sequence, one blue-sensitive, yellow-coupling silver halide emulsion layer, one green-sensitive, magenta-coupling silver halide emulsion layer and one red-sensitive, cyan-coupling silver halide emulsion layer; the yellow filter layer may be omitted.

The number and arrangement of the photosensitive layers may be varied in order to achieve specific results. For example, all high sensitivity layers may be grouped together in one package of layers and all low sensitivity layers may be grouped together in another package of layers in order to increase sensitivity (DE-25 30 645).

The substantial constituents of the photographic emulsion layers are binder, silver halide grains and colour couplers.

Details of suitable binders may be found in Research Disclosure 37254, part 2 (1995), page 286 and in Research Disclosure 38957, part II.A (1996), page 598.

Details of suitable silver halide emulsions, the production, ripening, stabilisation and spectral sensitisation thereof, including suitable spectral sensitisers, may be found in Research Disclosure 37254, part 3 (1995), page 286, in Research Disclosure 37038, part XV (1995), page 89 and in Research Disclosure 38957, part V.A (1996), page 603.

Photographic materials with camera sensitivity conventionally contain silver bromideiodide emulsions, which may optionally also contain small proportions of silver chloride. Photographic print materials contain either silver chloride-bromide emulsions with up to 80 wt. % of AgBr or silver chloride-bromide emulsions with above 95 mol. % of AgCl.

Details relating to colour couplers may be found in Research Disclosure 37254, part 4 (1995), page 288, in Research Disclosure 37038, part II (1995), page 80 and in Research Disclosure 38957, part X.B (1996), page 616. The maximum absorption of the dyes formed from the couplers and the developer oxidation product is preferably within the following ranges: yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 to 700 nm.

In order to improve sensitivity, grain, sharpness and colour separation in colour photographic films, compounds are frequently used which, on reaction with the developer oxidation product, release photographically active compounds, for example DIR couplers which eliminate a development inhibitor.

Details relating to such compounds, in particular couplers, may be found in Research Disclosure 37254, part 5 (1995), page 290, in Research Disclosure 37038, part XIV (1995), page 86 and in Research Disclosure 38957, part X.C (1996), page 618.

Colour couplers, which are usually hydrophobic, as well as other hydrophobic constituents of the layers, are conventionally dissolved or dispersed in high-boiling organic solvents. These solutions or dispersions are then emulsified into an aqueous binder solution (conventionally a gelatine solution) and, once the layers have dried, are present in the layers as fine droplets (0.05 to 0.8 &mgr;m in diameter).

Suitable high-boiling organic solvents, methods for the introduction thereof into the layers of a photographic material and further methods for introducing chemical compounds into photographic layers may be found in Research Disclosure 37254, part 6 (1995), page 292.

The non-photosensitive interlayers generally located between layers of different spectral sensitivity may contain agents which prevent an undesirable diffusion of developer oxidation products from one photosensitive layer into another photosensitive layer with a different spectral sensitisation.

Suitable compounds (white couplers, scavengers or DOP scavengers) may be found in Research Disclosure 37254, part 7 (1995), page 292, in Research Disclosure 37038, part III (1995), page 84 and in Research Disclosure 38957, part X.D (1996), pages 621 et seq.

The photographic material may also contain UV light absorbing compounds, optical brighteners, spacers, filter dyes, formalin scavengers, light stabilisers, anti-oxidants, Dmin dyes, plasticisers (latices), biocides and additives to improve the stability of dyes and couplers, to reduce colour fogging and to reduce yellowing and others. Suitable compounds may be found in Research Disclosure 37254, part 8 (1995), page 292, in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), pages 84 et seq. and in Research Disclosure 38957, parts VI, VIII, IX and X (1996), pages 607 and 610 et seq.

The layers of colour photographic materials are conventionally hardened, i.e. the binder used, preferably gelatine, is crosslinked by appropriate chemical methods.

Suitable hardener substances may be found in Research Disclosure 37254, part 9 (1995), page 294, in Research Disclosure 37038, part XII (1995), page 86 and in Research Disclosure 38957, part II.B (1996), page 599.

Once exposed with an image, colour photographic materials are processed using different processes depending upon their nature. Details relating to processing methods and the necessary chemicals are disclosed in Research Disclosure 37254, part 10 (1995), page 294, in Research Disclosure 37038, parts XVI to XXIII (1995), pages 95 et seq. and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), pages 630 et seq. together with example materials.

Compounds of the formula (III) are preferably used as dye stabilisers

in which

R31 denotes H, alkyl, alkenyl, aryl or acyl,

R32 denotes H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and

R33 denotes H, alkyl, alkenyl, aryl, acyl or chlorine,

wherein two or more residues R32 and R33 may be identical or different.

Typical examples of compounds of the formula (III) are

The compounds of the formula (III) are preferably used together with the compounds of the formulae (I) and (II) in the same layer.

EXAMPLE

Layer Structure 1

A colour photographic recording material was produced by applying the following layers in the stated sequence onto a layer support made from paper coated on both sides with polyethylene. Quantities are all stated per 1 m2. The silver halide application rate is stated as the corresponding quantities of AgNO3.

Layer 1: (Substrate layer) 0.10 g of gelatine Layer 2: (Blue-sensitive layer) Blue-sensitive silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % bromide, average grain diameter 0.9 &mgr;m) prepared from 0.46 g of AgNO3 with 0.70 mg of blue sensitiser BS-1 0.30 mg of stabiliser ST-1 1.25 g of gelatine 0.48 g of yellow coupler Y-1 0.20 g of image stabiliser BST-1 0.50 g of oil former OF-1 Layer 3: (Interlayer) 1.10 g of gelatine 0.06 g of DOP scavenger EF-1 0.06 g of DOP scavenger EF-2 0.12 g of tricresyl phosphate (TCP) Layer 4: (Green-sensitive layer) Green-sensitised silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % bromide, average grain diameter 0.47 &mgr;m) prepared from 0.26 g of AgNO3 with 0.70 mg of green stabiliser GS-1 0.50 mg of stabiliser ST-2 0.77 g of gelatine 0.24 g of magenta coupler M-1 0.20 g of image stabiliser BST-2 0.09 g of image stabiliser BST-3 0.24 g of dibutyl phthalate DBP) 0.24 g of isotetradecanol Layer 5: (UV protective layer) 0.95 g of gelatine 0.50 g of UV absorber UV-1 0.03 g of DOP scavenger EF-1 0.03 g of DOP scavenger EF-2 0.15 g of oil former OF-2 0.15 g of TCP Layer 6: (Red-sensitive layer) Red-sensitised silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % bromide, average grain diameter 0.5 &mgr;m) prepared from 0.30 g of AgNO3 with 0.03 mg of red sensitiser RS-1 0.60 mg of stabiliser ST-3 1.00 g of gelatine 0.35 g of cyan coupler C-1 0.70 g of dibutyl adipate Layer 7: (UV protective layer) 0.30 g of gelatine 0.20 g of UV absorber UV-2 0.10 g of oil former OF-3 Layer 8: (Protective layer) 0.90 g of gelatine 0.05 g of optical brightener WT-1 0.07 g of mordant (polyvinylpyrrolidone) 1.20 mg of silicone oil 2.50 mg of spacers (polymethyl methacrylate, average particle size 0.8 &mgr;m) 0.30 g of hardener H-1

Compounds used in layer structure 1:

OF-1

Polyester prepared from HOOC—(CH2)4—COOH, &eegr; (20° C.): 4000-5000 mPa.s HO—CH2—C(CH3)2—CH2—OH and C10H21—i nD (20° C.): 1.464-1.467

Layer Structures 2 to 10

Layer structures 2 to 10 correspond to layer structure 1 with regard to layer structure and composition and differ only in that the cyan coupler C-1 and TCP in layer 6 were replaced with the substances stated in Table 1. In samples 4, 9 and 10, the silver application rate was additionally reduced to 0.30 g/m2.

The samples were exposed through a step wedge, wherein colour filters were placed in the beam path in such a manner that only the red-sensitive layer was exposed. Processing was then performed as follows:

a) Colour developer - 45 s - 35° C. Tetraethylene glycol 20.0 g N,N-diethylhydroxylamine 2.0 g N,N-bis-(2-sulfoethyl)hydroxylamine, disodium salt 2.0 g N-ethyl-N-(2-methanesulfonamidoethyl)-4-amino-3-methyl- 5.0 g benzene sulfate Potassium sulfite 0.2 g Potassium carbonate 30.0 g Hydroxyethanediphosphonic acid 0.2 g Polymaleic anhydride 2.5 g Optical brightener (4,4′-diaminostilbenesulfonic acid 2.0 g derivative) Potassium bromide 0.02 g make up to 1000 ml with water; adjust pH to 10.2 with KOH or H2SO4 b) Bleach/fixing bath - 45 s 35° C. Ammonium thiosulfate 75.0 g Sodium hydrogen sulfite 13.5 g Ethylenediaminetetraacetic acid (iron/ammonium salt) 45.0 g make up to 1000 ml with water; adjust pH to 6.0 with ammonia (25 wt. %) or acetic acid. c) Rinsing - 90 s - 33° C. d) Drying

Maximum density (Dmax) and gradation (&ggr;) were then measured (Table 2). The percentage magenta density (Ndmagenta) at Dcyan=1.0 and the absorption maximum (&lgr;max) were also determined (Table 2).

The samples were furthermore exposed to 10·106 lux.h of light from a daylight-standardised xenon lamp. The percentage decrease in density at an initial density Dcyan of 1.0 was determined (&Dgr;D1.0, Table 2).

The samples were moreover stored in the dark for 42 days at 85° C. and 60% relative humidity and the percentage decrease in maximum density (Dmax) determined (Table 2).

TABLE 1 (C = comparison; I = according to the invention) Coupler Oil former Layer structure Compound mg/m2 mg/m2  1 (C) C-1 350 TCP 700  2 (C) I-8 300 TCP 600  3 (C) I-8 300 V-1/TCP 400/200  4 (C) I-3 300 V-2 600  5 (I) I-8 300 II-1/TCP 400/200  6 (I) I-8 300 II-7 600  7 (I) I-8 300 II-13 600  8 (I) I-8 300 II-14 600  9 (I) I-3 300 II-13 600 10 (I) I-3 300 II-19/TCP 400/200 TABLE 1 (C = comparison; I = according to the invention) Coupler Oil former Layer structure Compound mg/m2 mg/m2  1 (C) C-1 350 TCP 700  2 (C) I-8 300 TCP 600  3 (C) I-8 300 V-1/TCP 400/200  4 (C) I-3 300 V-2 600  5 (I) I-8 300 II-1/TCP 400/200  6 (I) I-8 300 II-7 600  7 (I) I-8 300 II-13 600  8 (I) I-8 300 II-14 600  9 (I) I-3 300 II-13 600 10 (I) I-3 300 II-19/TCP 400/200

The following were used as comparison compounds

As Table 2 shows, using the coupler according to the invention (I) gives rise to a cyan image having improved dark storage stability relative to C-1.

However, colour reproduction and light stability are then unsatisfactory. Only when compounds according to the invention of the formula (II) are simultaneously used is satisfactory light stability achieved together with colour reproduction which is even distinctly improved relative to C-1.

Claims

1. A color photographic material which comprises at least one silver halide emulsion layer sensitized for the red range of the spectrum, which layer contains associated therewith at least one compound of the formula (I) in which R 11 and R 12 mutually and independently denote an electron-attracfing group, X 11 denotes H or a group separable on reaction with the developer oxidation product, y 11 denotes a group to complete a nitrogenous heterocycle, providing that a group represented by R 12 is attached to a carbon atom of the heterocycle, n denotes 1 or 2, and at least one pound of the formula (II-A) in which R 23 and R 24 mutually and independently denote alkyl, acyl, acylamino, alkoxy, halogen, cyano or nitro, R 25 denotes H or alkyl, R 26 denotes H, alkyl or acyl and r and s mutually and independently denote 0, 1 or 2 providing that the compound contains a total of at least 16 C atoms. 2. The color photographic material according to claim 1, wherein the compounds of the formula (I) comprise the compound of the formula (I-A); in which R 13 and R 14 mutually and independently have the meaning of R 11 or R 12, X 12 has the meaning of X 11 and Z 12 denotes H or a substituent. 3. The color photographic material according to claim 1, wherein the compound of the formula (I) Ls in a quantity of 50 to 500 mg/m 2 of the photographic recording material. 4. The color photographic material according to claim 1, wherein it contains the compounds of the formula (II-A) are present in a weight ratio of 20:1 to 1:10 relative to the compound of the formula (I). 5. The color photographic material according to claim 1, which further comprises compounds of the formula (III) in which R 31 denotes H, alkyl, alkenyl, aryl or acyl, R 32 denotes H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and R 33 denotes H, alkyl, alkenyl, aryl, acyl or chlorine, wherein two or more residues R 32 and R 33 may be identical or different. 6. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are present in a red-sensitized silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer. 7. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are used in the same layer. 8. The color photographic material according to claim 6, wherein the compounds of the formulae (I), (II-A) and (III) are present in the same layer. 9. The color photographic material, as claimed in claim 1, wherein R 11 and R 12 mutually and independently denote an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulfonylmethyl, arylsulfonylmethyl, a nitro group, a halogen atom and X 11 is halogen, N-linked, optionally substituted N-heteroaromatics, non-aromatic heterocyclics, S-linked aliphatic or aromatic mercaptans or O-linked aliphatic or aromatic hydroxy compounds. 10. The color photographic material according to claim 9, wherein X 11 is chlorine, pyrazole, imidazole, triazole, hydantoin, oxazolidinedione, mercaptopropionic acid, 2-acylaminophenyl mercaptan, ethylene glycol or p-salicyclic acid ethyl ester. 11. The color photographic recording material according to claim 1, wherein the compound of the formula I is in a quantity of 20 to 2,000 mg/m 2 of the photographic recording material. 12. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 10:1 to 1:5 relative to the compounds of formula I. 13. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 5:1 to 1:2 relative to the compounds of formula.

2. The color photographic material according to claim 1, wherein the compounds of the formula (I) comprise the compound of the formula (I-A); in which R 13 and R 14 mutually and independently have the meaning of R 11 or R 12, X 12 has the meaning of X 11 and Z 12 denotes H or a substituent. 3. The color photographic material according to claim 1, wherein the compound of the formula (I) Ls in a quantity of 50 to 500 mg/m 2 of the photographic recording material. 4. The color photographic material according to claim 1, wherein it contains the compounds of the formula (II-A) are present in a weight ratio of 20:1 to 1:10 relative to the compound of the formula (I). 5. The color photographic material according to claim 1, which further comprises compounds of the formula (III) in which R 31 denotes H, alkyl, alkenyl, aryl or acyl, R 32 denotes H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and R 33 denotes H, alkyl, alkenyl, aryl, acyl or chlorine, wherein two or more residues R 32 and R 33 may be identical or different. 6. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are present in a red-sensitized silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer. 7. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are used in the same layer. 8. The color photographic material according to claim 6, wherein the compounds of the formulae (I), (II-A) and (III) are present in the same layer. 9. The color photographic material, as claimed in claim 1, wherein R 11 and R 12 mutually and independently denote an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulfonylmethyl, arylsulfonylmethyl, a nitro group, a halogen atom and X 11 is halogen, N-linked, optionally substituted N-heteroaromatics, non-aromatic heterocyclics, S-linked aliphatic or aromatic mercaptans or O-linked aliphatic or aromatic hydroxy compounds. 10. The color photographic material according to claim 9, wherein X 11 is chlorine, pyrazole, imidazole, triazole, hydantoin, oxazolidinedione, mercaptopropionic acid, 2-acylaminophenyl mercaptan, ethylene glycol or p-salicyclic acid ethyl ester. 11. The color photographic recording material according to claim 1, wherein the compound of the formula I is in a quantity of 20 to 2,000 mg/m 2 of the photographic recording material. 12. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 10:1 to 1:5 relative to the compounds of formula I. 13. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 5:1 to 1:2 relative to the compounds of formula.

3. The color photographic material according to claim 1, wherein the compound of the formula (I) Ls in a quantity of 50 to 500 mg/m 2 of the photographic recording material.

4. The color photographic material according to claim 1, wherein it contains the compounds of the formula (II-A) are present in a weight ratio of 20:1 to 1:10 relative to the compound of the formula (I).

5. The color photographic material according to claim 1, which further comprises compounds of the formula (III) in which R 31 denotes H, alkyl, alkenyl, aryl or acyl, R 32 denotes H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and R 33 denotes H, alkyl, alkenyl, aryl, acyl or chlorine, wherein two or more residues R 32 and R 33 may be identical or different. 6. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are present in a red-sensitized silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer. 7. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are used in the same layer. 8. The color photographic material according to claim 6, wherein the compounds of the formulae (I), (II-A) and (III) are present in the same layer. 9. The color photographic material, as claimed in claim 1, wherein R 11 and R 12 mutually and independently denote an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulfonylmethyl, arylsulfonylmethyl, a nitro group, a halogen atom and X 11 is halogen, N-linked, optionally substituted N-heteroaromatics, non-aromatic heterocyclics, S-linked aliphatic or aromatic mercaptans or O-linked aliphatic or aromatic hydroxy compounds. 10. The color photographic material according to claim 9, wherein X 11 is chlorine, pyrazole, imidazole, triazole, hydantoin, oxazolidinedione, mercaptopropionic acid, 2-acylaminophenyl mercaptan, ethylene glycol or p-salicyclic acid ethyl ester. 11. The color photographic recording material according to claim 1, wherein the compound of the formula I is in a quantity of 20 to 2,000 mg/m 2 of the photographic recording material. 12. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 10:1 to 1:5 relative to the compounds of formula I. 13. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 5:1 to 1:2 relative to the compounds of formula.

6. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are present in a red-sensitized silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer.

7. The color photographic material according to claim 1, wherein the compounds of the formulae (I) and (II-A) are used in the same layer.

8. The color photographic material according to claim 6, wherein the compounds of the formulae (I), (II-A) and (III) are present in the same layer.

9. The color photographic material, as claimed in claim 1, wherein R 11 and R 12 mutually and independently denote an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl sulfonyl, sulfinyl, sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulfonylmethyl, arylsulfonylmethyl, a nitro group, a halogen atom and X 11 is halogen, N-linked, optionally substituted N-heteroaromatics, non-aromatic heterocyclics, S-linked aliphatic or aromatic mercaptans or O-linked aliphatic or aromatic hydroxy compounds.

10. The color photographic material according to claim 9, wherein X 11 is chlorine, pyrazole, imidazole, triazole, hydantoin, oxazolidinedione, mercaptopropionic acid, 2-acylaminophenyl mercaptan, ethylene glycol or p-salicyclic acid ethyl ester.

11. The color photographic recording material according to claim 1, wherein the compound of the formula I is in a quantity of 20 to 2,000 mg/m 2 of the photographic recording material.

12. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 10:1 to 1:5 relative to the compounds of formula I.

13. The color photographic recording material according to claim 4, wherein the compounds of the formula (II-A) are present in a weight ratio of 5:1 to 1:2 relative to the compounds of formula.